Enzyme containing detergent composition having improved physical and stability characteristics

ABSTRACT

An enzyme containing granular detergent composition having improved physical and stability characteristics which is comprised of a water-soluble inorganic or organic builder, an enzyme and water-soluble alkali metal salt, ester, or C1-2 alkylor alkylolomide of a copolymer of maleic anhydride and a vinyl compound of the formula RCH - HCR, wherein one R represents a hydrogen atom, while the other R represents a C1-4 alkyl ether radical, or a hydrogen atom.

AU 165 Ex U llllefl mates rawur Zaki et al. [451 Apr. 11, 1972 541 ENZYME CONTAINING DETERGENT [56] References Cited COMPOSITION HAVING IMPROVED PHYSICAL AND STABILITY UNTEDSTATES PATENTS CHARACTERISTICS 3,485,762 12/ 1969 Gower et al. ..252/ l 35 2,702,277 2/1955 Kinney ..252/135 [72] Inventors: Wahib Nasslf Zaki, 668 Avenue de Tervueren, Brussels, Belgium; Jean Marie OTHER PUBLICATIONS Louis Coulomb Residence Puccini, Rue Antione di Dorzinico Maniques, France; lgCgalmtrez Alwi2 General Aniline & Film Corp., N.Y., N.Y. Peter Lovgren, Holmelundsvej s, 2650 I Hvldovre Copenhagen Denmark Pn'mary Examiner-Mayer Weinblatt [22] Filed: Jan. 5, 1970 Attorney-Julius P. Filcik [2]] Appl. No.: 797 [57] ABSTRACT An enzyme containing granular detergent composition having [30] Fomgn Application Pnomy Data improved physical and stability characteristics which is mm Jan. 10, l969 France ..6900346 ri d of a water-soluble inorganic or organic builder, an enzyme and water-soluble alkali metal salt, ester, or C alkylor Cl 2/DlG. l2, alkylolomide of a copolymer of maleic anhydride and a vinyl 252/D 252/523 compound of the formula RCH HCR, wherein one R [5 l] represents a hydrogen atom the other R represents a C Fleld of Search 2, 4 ether radical or a hydrogen atom 6 Claims, N0 Drawings ENZYME CONTAINING DETERGENT COMPOSITION HAVING IMPROVED PHYSICAL AND STABILITY CHARACTERISTICS The present invention pertains to a granular or powdered free flowing detergent composition containing enzymes, and optionally hydrogen peroxide addition compounds; and, to an improved process for manufacturing the same.

Adapting the composition of granular or powdered detergent compositions intended to improve the storage stability, the detergency power, and to reduce the stickiness and caking has been extensively done, developed and used. Increasing of the production rate without decreasing said properties, or without changing the profile or characteristics of the end product, has always been highly desirable.

Storage stability, i.e., color, thermal and hygroscopic stability is lacking in many granular or powdered detergent compositions. Stability in color, etc., is particularly necessary for granuluar or powdered detergent compositions subjected to different environmental conditions, due to prolonged storage, and for granular or powdered detergent compositions to be distributed in countries having climatologically different areas.

Stickiness or caking of a granular or powdered detergent composition is mainly influenced by the concentration of the surface-active agent incorporated in said detergent composition. When suds depressants, for example, water-soluble nonionic alkylene oxide adducts, are to be incorporated in the detergent composition, the concentration of surface-active agent has to be lowered, to avoid stickiness and caking. This entails decrease in detergency power of the granular or powdered detergent compositions but does not always solve the stickiness or caking problem. Moreover, many attempts to avoid caking and stickiness, or to increase stability of a granular or powdered detergent composition impaired or adversely affected other desirable properties. For example, ethylenediaminetetraacetic acid or the salts thereof, added into a granular detergent composition to improve its detergency, adversely affects the bleaching capacity of sodium perborate present in such a detergent composition.

Enzymes, highly desirable in an all-purpose detergent composition, are usually in a concentrated fine powdered form. Such fine powders are difficult to handle, to measure, to formulate, and tend to segregate. Moisture, i.e., water, added to bind said enzyme powders, tends to cause the enzymes to degrade themselves. Consequently, when incorporated in a detergent composition, the composition is charged with impurities instead of active enzymes. A maleic anhydride-vinyl methyl ether copolymer, when mixed as such with a granular or powdered detergent composition for improving whiteness maintenance, decreases the activity of the enzymes substantially, and when mixed with detergent compositions containing perborates, to improve the bleaching activity of the latter, also causes severe discoloration and caking.

lt has now been found that a granular or powdered detergent composition comprising a surface-active agent selected from the group consisting of water-soluble organic, anionic, non-ionic, amphoteric, or zwitterionic detergents, and mixtures thereof (or an non-ionic" detergent); a water-soluble inorganic builder salt and optionally an organic builder salt; an enzyme product, i.e., pure enzyrng plus carrier; preferably hydrogen peroxide bleaching compoundi'a'nd, if desired, the usual additives, can be made stable, free flowing, without affecting adversely any other property, by incorporating from about 0.1% to about 8% by weight, calculated on a finished product basis, of an alkali-metal salt, ester, or C alkyl or alkylolamide of a copolymer of maleic anhydride and a vinyl compound of the formula RCH HCR, wherein one R represents a hydrogen atom, while the other R represents a C,-, alkyl ether radical, preferably a OCH, radical, or a hydrogen atom.

The present invention consequently pertains to a granular or powdered, free flowing detergent composition comprising of from to about 50% by weight of a surface active agent LII selected from the group consisting of an organic water-soluble anionic, non-ionic, amphoteric, or zwitterionic detergent or mixtures thereof; from about 10% to about by weight of a water-soluble, inorganic builder salt, or mixtures thereof, alone, or in combination with a water-soluble organic builder salt, or mixtures thereof; from about 0.1% to about 8% by weight of a water-soluble alkali-metal salt, ester, or C -3 alkylor alkylolamide of a copolymer of a maleic anhydride and a vinyl compound of the formula RCH HCR, wherein one R represents a hydrogen atom, while the other R represents a C alkyl ether radical or a hydrogen atom; from about 0.01% to about 5% by weight of an enzyme product; and, optionally, from about 5% to about 50% by weight of an organic and preferably inorganic hydrogen peroxide addition compound.

Preferred is a granular or powdered detergent composition containing from 5% to about 25% by weight of a water-soluble non-cationic detergent (preferably the sodium salts of C alkyl-benzene sulfonates or the sodium salts of higher fatty alcohol sulfates); from about 10% to about 50% by weight of a water-soluble inorganic builder salt (preferably sodium tripolyphosphate); from about 8% to about 38% by weight of a water-soluble inorganic hydrogen peroxide addition compound (preferably sodium perborate tetrahydrate); from about 0.1% to about 3.0% by weight of enzyme product, and from about 0.3% to about 5.0% by weight of a water-soluble alkali-metal salt of a maleic anhydride-vinyl methyl ether copolymer.

In one of its aspects, the invention comprises the use of a water-soluble alkali-metal salt, ester, or c, alkylor alkyl-or alkylolamide of a maleic anhydride-ethylene or vinyl C,-, alkyl ether copolymer. The degree of polymerization of said copolymer adequately soluble under regular use conditions is difficult to establish. There is a recognized correlation between the viscosities of polymeric compounds and their relative molecular weights or degree of polymerization. Therefore, since viscosity figures are generally more meaningful and can be obtained easily, the copolymers described in the present application are characterized either in terms of their specific viscosity or in centipoises, whereby the figures given pertain to the anhydride form.

The specific viscosity of the anhydride form of the maleic anhydride-vinyl C alkyl ether copolymer preferably varies between 0.1 and 6.0, most preferably between 0.2 and 5.0; the specific viscosity is defined by measuring the viscosity of the solution of lg. of the anhydride-copolymer in cc. methylethylketone in a Cannon-Fenske (Series 100) viscosity meter at 25 C. The viscosity of the maleic anhydride-ethylene copolymer varies preferably between 1.2 and 10 centipoises when measured as an aqueos solution containing 2 percent of the copolymer in a Brookfield RTV viscosity meter at 10 r.p.m., at 25 C., whereby the solution is adjusted to have a pH of 10.

The copolymer which is used in the composition of the invention is preferably the sodium and potassium salt. Another valuable copolymer is the primary or secondary C alkyl amide or C alkylolamide and especially the monoand diethanolamide. The ester derivative of the copolymer is either the C and preferably the C,-, aliphatic alcohol reaction product, or the reaction product of the copolymer and a water-soluble organic compound having at least one reactive hydroxyl radical, for example, the water-soluble condensation product of 6 to 25 moles of ethylene oxide with a C aliphatic alcohol, with a C alkylsubstituted phenol, with condensated propylene oxide, or with the reaction product of propylene oxide and ethylene diamine. Preferably only 5 to 60 percent of the carboxylic acid radicals of the copolymer are esterified or reacted with a C,-, alkylor alkylolamine. The ratio of the monomers in the copolymers may vary from 2:1 to 1:2, but is preferably 1:1.

The enzyme product to be used according to the present invention contains catalytically active protein materials, which degrade or alter one or more types of soil or stains encountered in soaking and laundering situations, so as to remove the soil or stains from the fabric being soaked and/or laundered, or make the soil or stains removable in a subsequent laundering step, and an inert vehicle. Said enzyme products, preferably in a dry powdered form, contain from 2 to 80 percent, preferably from 6% to about 40% of active material.

The superiority of the granular or powdered detergent composition subject of the present invention, if compared to a similar composition, as illustrated by the following tests, whereby two series of different detergent compositions were prepared consisting of:

Components A B by wt. by wt. sodium alkylbenzene sulfonate 14.00% 950% (average C: ll.9) tallow alcohol-ethylene oxide condensate (avenge oxide units: 9-12) 3.00 2.00 fatty acids (derived from fish oil) 4.50 3.00 enzyme product 1.00 0.60 sodium tripolyphosphate 45.00 30.00 sodium silicate 8.00 5.00 sodium sulfate 8.00 6.00 carboxymethylcellulose L L00 sodium perborate-tetrahydrate 32.00 copolymer X 2.00 1.50 miscellaneous (perfume, brightener) 3.00 2.00 moisture balance balance enzyme product: ALCALASl-I," a proteolytic enzyme product. made by Novo lndustri AIS, Copenhagen, Denmark, containing 6% active enzyme.

All compositions were prepared by mixing the surface-active agent, fatty acid, builder salt, electrolyte, and carboxymethylcellulose in a crutcher, spray-drying the crutcher mixture, and admixing the copolymer, enzyme product, perfume, and sodium perborate-tetrahydrate.

Of both series of compositions A and B, four compositions contained the following copolymer:

IA and [B X sodium salt of maleic anhydride-vinyl methyl ether HA and [i8 X the anhydride of IA and IB;

lllA and "IE X 32 sodium salt of maleic anhydrideethylene;

IVA and NB X the anhydride of "IA and 1118.

The specific viscosity of the malaic anhydride-vinyl methyl ether use is 0.4, and the ratio of monomers 1:1; the viscosity of the maleic anhydride-ethylene copolymer is 2 c.p.s., and the ratio of monomers 1:].

TEST A Enzyme Activity Eight detergent compositions( A l-lV and B l-lV) were stored for 4 weeks under normal ambient temperatures. Each composition was then dissolved in water (concentration 1.5 percent by weight), heated to and maintained at 40 C. Defining the loss in enzyme activity of the eight detergent compositions, by the casein U V method, yielded the following results: no appreciable loss for IA, [8, [HA and H18, 55 percent for HA and over 20 percent for H8, a few percent for IVB, but over 93 percent for lVA.

Test B Discoloration:

Detergent compositions IB and H8, and a similar detergent composition but containing neither sodium perborate tetrahydrate nor copolymer, were stored during two weeks at 38 C. in an atmosphere of 80 percent relative humidity. After the 2 weeks the discoloration of each composition was mea sured with a Hunterlab D25 Color Difference Meter (Hunter Ass. Laboratory Inc., Virginia, U.S.A.) and a white standard ceramic tile as reference. The differences AE= vAa=+ab +AL2 whereby 1., i n d@tes the lightness and varies from 100 for perfect white to zero for black; a indicates redness when plus, gray when zero, and greenness when minus; and b measures yellowness when plus, gray when zero, and blueness when minus), revealed a change A5 of 2.0 for the test sample composition, a A5 2.2 for composition 18, and a A5 l 1.8 for composition IIB. Or a heavy, unpleasant yellowing, because the difference A5 l 1.8 was mainly due to the Ab of composition llB, occurred.

TEST C Pourability-stickiness Improved pourability and reduced stickiness of a granular or powdered detergent composition can best be evaluated by the avalanche test, and the compression and strength test.

1. in the avalanche test about 1.000 cc. of each composition is spread evenly in a curved trough open at both ends (depth of layer in the middle about 4 cm.). By lowering one end, the bulk of said granules slide off at a certain angle, which indicates the degree of pourability of the granules. The average angle for a very good free-flowing granular composition is 38, while an average of 44 and more indicates an unacceptable product.

2. The "compression test requires a cylinder (diameter length -l :3 which is filled with the granules and is tapped to settle the latter. Said granules are compressed by a piston of approximately the same diameter as the inner diameter of said cylinder, and having the same weight in each test. The change in length of each column of granules is measured after 5 minutes (compression). The compression is measured in percentage calculated on the initial length, 0 percent of compression indicating a perfect granular composition and over 12 percent indicating an unacceptable product.

3. The cake-strength" test is applied to the same compositions as used in the compression test, whereby the column of granules compressed during the compression test, is freed from the piston and the cylinder, and the force needed to break the compressed column is measured (cake strength). The cake strength is graded from 0 to 7, 0 being perfect, i.e., strong granules which do not stick together, and 7 being unacceptable.

Four granular detergent compositions, IA, "3, 11A, and B, stored during four weeks at 38 C., and at percent relative humidity, were tested according to the methods described hereabove. The results are presented in Table I.

According to Table l the detergent composition HA and "B are unacceptable, while the compositions lA and [B grade from very satisfactory (compression) to good (avalanche) to very good (cake strength).

From said avalanche, compression and cake strength test, it is also evident that the cleaning capacity of a detergent composition can be increased. The amount of surface-active agents that can be incorporated in a free-flowing granular or powdered composition is limited due to the stickiness and concentration of the surface-active agent. By the present invention the stickiness of a given detergent composition can be decreased substantially. Consequently, by the present invention the concentration of surface-active agent in a granular or powdered detergent composition can be increased without affeeting its pourability.

Further, when other sticky materials must be present in the detergent composition, for example, a nonionic as sudsdepressant, it is made possible by the present invention to incorporate said sticky material without lowering the concentration of the surface-active agent, and still to obtain an acceptable freesflowing detergent composition.

The detergent composition of the present invention can be manufactured by dry-mixing the different components, or by slurrying the components, followed by drying. The detergent composition can be prepared batch by batch, or continuously. The copolymer is preferably added in the slurry in its salt, ester, or amide form, but can be added in its anhydride form. If the latter occurs, the anhydride is to be converted into its salt, ester, or amide fonn in the slurry, by adding the necessary alkali metals, alcohols or amines. it is not preferred, however, to form the amide, ester, or salt derivative of the copolymer during the slurrying, because said method requires a meticulous and accurate control of the temperature, humidity and pH of the slurry, to avoid side reactions, which may change the profile or characteristics of the finished product.

Another surprising effect obtained during the manufacturing of the composition of the present invention is that the salt, ester, or amide derivative of the copolymer decreases the viscosity of the slurry. This entails that less energy is required to mix the slurry thoroughly, or that the capacity of the device, wherein the slurry is prepared, is increased. Further, due to said decreased viscosity, the blowing rate of the spray-tower, when said slurry is to be spray-dried, is increased too. Consequently, a preferred process for preparing a stable, freefiowing granulated detergent composition of the present invention is by slurrying the components followed by drying at low temperatures. The most preferred process is, however, slurrying the detergent, copolymer, builder, electrolyte and other non-heat sensitive compounds, spray-drying the slurry,

and dry mixing with, or spraying onto the granules the enzymes, hydrogen peroxide addition compounds if any, the perfume and other heat sensitive components.

Suitable enzymes to be used according to the present invention are those active at a pH range of from 4 to 12, preferably from 7 to l l, and at a temperature of from 10 to 85 C., preferably from 25 to 75 C. Said suitable enzymes can be grouped into five major classes:

I. those which catalyze the addition or removal of water, degrading thereby the soil, especially of a protein type:

1. hydrolyzing enzymes such as hydrolases, e.g., proteases,

esterases, carbohydrases and nucleases,

2. hydrating enzymes, e.g., hydrases;

ll those which catalyze the oxidation or reduction of a substrate, degrading oxidizable orreducible soil, the oxido-reductases, e.g., alcohol dehydrogenases, xanthine oxidases, amino acid oxidases;

Ill. those which transfer a radical from one radical to another, or transferases, e.g., transglycodases, transphosphorylases and -phosphormutases, transaminases, transmethylases and transacetylases;

lV. those which split or form bounds without group transfer or desmolases, e.g., ligases and lyases, and

V. those which isomerize and chemically alter a soil such as lipid and carbohydrate soil isomerases, e.g., racemases and epimerases, cis-trans-isomerases, intramolecular transferases and oxido-reductases. in a few cases a single enzyme may fit more than one of these classes.

in summary the hydrolases, hydrases, oxidoreductases and desmolases degrade soil to remove it or make it more removable and the transferases and isomerases alter soil so as to make it more removable. Of these classes the hydrolases and particularly the proteases, esterases, carbohydrases and nucleases, with the proteases having the broadest range of soil degradation capability are preferred. Mixtures of the enzymes may be used if desired. Specific examples of proteases suitable for use in this invention are pepsin, trypsin, chymotrupsin, collagenase, keratinase, elastase, subtilisin, papain, bromelin, carboxy peptidase A and B, amino peptidase, aspergillopeptidase A and aspergillopeptidase B. Preferred proteases are serine proteases which are active in the neutral to alkaline pH range and one produced from microorganisms such as bacteria, fungi or mold. The serine proteases which are procured by mammalian systems, e.g., pancreatin, are useful in acid situations.

Specific examples of the esterases are gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotases.

Specific examples of carbohydrases are maltase, saccharase, amylases, cellulase, pectinase, lysozyme, aglycosidase and B-glycasidase.

Two specific examples of nucleases are ribonuclease and desoxyribonuclease.

The enzyme products utilized in this invention are generally obtained and stored in a dry, powdered form. They can be mixed as such with the components forming the detergent composition or adsorbed on a carrier, together with nonionie compounds, or slurried in water. The dry, powdered form is most easily handled and generally is more stable than enzymes in a water slurry.

The commercial powdered enzyme products are generally dry powdered products comprising 2 to percent active enzymes in combination with an inert powdered vehicle such as sodium or calcium sulfate or sodium chloride, clay or starch as the remaining 98-20 percent. Active enzyme content of a commercial product is a result of manufacturing methods employed and is not critical herein so long as the laundry product has the desired enzymatic activity. Many of these commercial products contain the preferred proteases as the active enzyme product. In most cases, a subtilisin comprises the major portion of the proteases; other examples of hydrolase generally included in commercial products are lipases, carbohydrases, esterases and nucleases.

Specific examples of commercial enzyme products and the manufacturer thereof include: Alcalase, Novo Industri, Copenhagen, Denmark; Maxatase, Koninklijke Nederlandse Gist en Spiritusfabriek N.V., Delft, Netherlands; Protease B-4000 and Protease AP, Schweizerische Ferment A.G., Basel, Switzerland, CRD-Protease, Monsanto Company, St. Louis, Missouri, Vickase, Viobin Corporation, Monticello, lllinois; Pronase-P, Pronase-AS and Pronase-AF, all of which are manufactured by Kaken Chemical Company, Japan; Rapidase P-2000, Rapidase, Seclin, France; proteolytic enzyme products (particle size 1 mm. 0.1 mm.) manufactured by Clinton Corn Products, Division of Standard Brands, New York; Takamine, Bromelain 1:10, HT proteolytic enzyme 200, Enzyme L-W (derived from fungi rather than bacteria), Miles Chemical Company, Elkhart, Indiana; Rhozym P-ll concentrate, Pectinol, Lipase B, Rhozyme PF, Rhozyme J-25, Rohm and Haas, Philadelphia, Pennsylvania (Rhozyme RF and 1-25 have salt and cornstarch vehicles and are proteases having diastase activity); Amprozyme 200, Jacques Wolf & Company, a subsidiary of Nopco Chemical Company, Newark, New Jersey.

CRD Protease (also known as Monsanto DA-IO) is a useful powdered enzyme product. CRD-Protease is reported to be obtained by mutation of a Bacillus Subtilis organism. It is about 80 percent neutral protease and 20 percent alkaline protease. The neutral protease has a molecular weight of about 44,000 and contains from one to two atoms of zinc per molecule. its particle size ranges predominantly from 0.03 mm. to 0.1 mm. The CRD-Protease can be used in an aqueous system having a pH ranging from about 5.4 to about 8.9. It can be prepared to range in active enzyme content from 20 to 75 percent. The presence of CaCl in the enzyme powder increases the pH range over which the enzyme can be utilized. This enzyme can be utilized in the composition of this invention with excellent results in washing solutions at temperatures ranging from about 10 to about 66 C., and at lower pHs suitable for prewash soaking or higher pHs for detergency purposes.

Pronase-P, Pronase-As and Pronase-AF are powdered en- I zyme products which can also be used to advantage in this invention. These enzymes are produced from the culture broth of Streptomyces griseus used for streptomycin manufacture.

They are isolated by the successive resin column treatment. The major component of the pronase is a neutral protease named as Streptomyces griseus protease. This enzyme product contains a calcium stabilizer salt and is fairly stable over a wide pH range, e.g., 4 to 10, and is fairly stable over a temperature range of 10 to 66 C.

Another enzyme product preferred for use in the detergent compositions of this invention, including a number of the Examples, is a proteolytic enzymes, a serine protease, manufactured by Novo lndustri A/S, Copenhagen, Denmark, and sold under the trade name of Alcalase. Alcalase is described, in a trade bulletin bearing that name which was published by Novo lndustri A/S, as a proteolytic enzyme preparation manufactured by submerged fermentation of a special strain of Bacillus Subtilis. The primary enzyme component of Alcalase is subtilisin. In addition to proteolytic activity, Alcalase exhibits other forms of desirable enzymatic activity. Alcalase is a fine grayish powder having a crystalline active enzyme content of about 6 percent and a particle size ranging from 1.2 mm. to 0.01 mm. and smaller, about 75 percent passing through a 100 mesh Tyler screen. The remainder of the powder is comprised primarily of sodium chloride, calcium sulfate and various inert organic vehicle materials. Alcalase has unusually stable propenies in solution. For example, Alcalase can withstand a pH of about 9 at relatively high temperatures, i.e., 66-77 C., for a short time. At 49 C., the activity of Alcalase is virtually unchanged in a 24-hour period when held at this pH. Alcalase can be advantageously used with soap and detergent compositions of this invention.

The particular enzyme product chosen for use in the products and process of this invention depends on the conditions of final utility, including carrier pH, composition pH, use pH, use temperature and soil types to be degraded or altered. The enzyme can be chosen to provide optimum activity and/or stability for any given set of usage conditions.

The powdered enzyme product can be attached to a granular carrier in the detergent composition and process of this invention to provide from about 0.001 percent to about 3 preferably 0.01 to 1.5 percent of pure enzyme, calculated on the total weight of enzyme powder and carrier. When the carrier with enzyme product is uniformly blended with detergent granules to form a detergent composition, the enzyme product concentration usually ranges from 0.01 to percent, generally 0.1 to 3 percent of the detergent composition. Taking into account the inert vehicle in commercial powdered enzyme products, the amount of enzyme products (enzyme vehicle) attached to the granular carrier can range up to 40 percent, preferably to 20 percent, of the total weight of enzyme products plus carrier. The enzyme products can also be dissolved in water, and sprayed onto the finished detergent composition, or to one or more components of said composition to provide from 0.01% to about 5%, preferably 0.1-3 percent of the total detergent composition.

The water-soluble surface-active agent which can be utilized in the composition of this invention are soap and anionic, nonionic, ampholytic and switterionic synthetic detergents and mixtures thereof. These suitable surface-active agents are enumerated below.

a. Water-soluble soap: the sodium, potassium, ammonium and alkanol ammonium (e.g., triethanolammonium) salts of higher fatty acids containing from to 22 carbon atoms.

b. anionic synthetic non-soap detergents: a preferred class, can be broadly described as the water-soluble salts, particularly the alkali-metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from eight to 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical (included in the term alkyl is the alkyl portion of higher acyl radicals). Preferred are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-cm carbon atoms) and sodium or potassium C alkyl benzene sulfonates, sodium alkyl glyceryl ether sulfonates;

sodium coconut oil fatty acid monoglyoeride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and l to 6 moles of ethylene oxide, sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from eight to 12 carbon atoms; the reaction product of C fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, and others known in the art.

c. Nonionic synthetic detergents: broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound; which may be aliphatic or alkyl aromatic in nature. Preferred classes of nonionic synthetic detergents are as follows:

1. Compounds formed by condensing ethylene oxide with a hydrophobic base, formed by the condensation of propylene oxide with propylene glycol, whereby said hydrophobic portion of the molecule has a molecular weight of from about 1,500 to 1,800, while the polyoxyethylene content is about 50 percent of the total weight of the condensation product 2. The polyethylene oxide condensates of C alkyl phenols with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.

3 Nonionic synthetic detergents derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from 40 to percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide; said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.

4. The condensation product of aliphatic alcohols having from eight to 22 carbon atoms with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

5. The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about eight to about 18 carbon atoms.

6. Long chain tertiary amine oxides correspond to the following general formula:

wherein R is an alkyl radical of from about eight to about 24 carbon atoms, R and R are each methyl, ethyl, or hydroxyethyl radicals, R is ethylene, and n is 0 or an integer of up to 10. The arrow in the formula is a conventional representation of a semi-polar bond. Specific examples of amine oxide detergents include: dimethyl dodecyl amine oxide; acetyl dirnethyl amine oxide; bis-(2-hydroxyethyl) dodecyl amine oxide; bis- (Z-hydroxyethyl) 3-dodecoxy-l-hydroxypropyl amine oxide.

7. Long chain tertiary phosphine oxides corresponding to the following general fon'nula RR'R"PO wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 24 carbon atoms in chain length and R and R are each alkyl or monohydroxyalkyl groups containing from one to three carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are found in British Pat. No. 995,260, and include: dimethy] dodecyl phosphine oxide; diethyl dodecyl phosphine oxide; and dimethy Z-hydroxy-dodecyl phosphine oxide.

8. Long chain sulfoz'ides having the formula wherein R is an alkyl radical containing from 10 to 28 carbon atoms, from to ether linkages and from 0 to 2 hydroxyl substituents, at least one moiety of R being an alkyl radical containing no ether linkages and containing from to 18 carbon atoms, and wherein R is an alkyl radical containing from one to three carbon atoms and from 1 to 2 hydroxyl groups. Specific examples of these sulfoxides are: 3-methoxy tridecyl methyl sulfoxide: 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

d. Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, wherein one of the aliphatic substituents contains from eight to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulpho, sulphato, phosphate or phosphono. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3-dodecylamino-propane sulfonate.

e. Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds, wherein one of the aliphatic substituents contains from eight to 18 carbon atoms arid one contains an anionic water solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato, or phosphono. Examples of compounds falling within this definition are 3-(N,N- dimethyl-N-hexadecylammonio) propane-l-sulfonate and 3- (N,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-lsulfonate which are especially preferred for their excellent cool water detergency characteristics. See, for example, British Pat. No. 987,795. A suitable, water-soluble inorganic builder salt or mixtures thereof, used alone or in combination with a water-soluble organic builder salt, or mixtures thereof, is an alkali-metal phosphate, polyphosphate, carbonate, borate, bicarbonate and silicate (an ammonium and substituted ammonium salt can also be used). Specific examples of such an inorganic builder salt are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate and the corresponding potassium salts, sodium hexametaphosphate, sodium sesquicarbonate and sodium monoand di-orthophosphate.

Examples of a suitable organic, water-soluble builder salt are alkali-metal, ammonium or substituted ammonium polycarboxyl-ates, e.g., sodium and potassium ethylenediaminetetraacetates or nitriloacetates, and the sodium and potassium lower alkyl di-phosphonates such as trisodiurn ethylene l -hydroxy-l l -diphosphonate.

Examples of a suitable hydrogen peroxide addition compound are the perborates, e.g., the sodium perborate monoand tetrahydrate, further the potassium perborates ZKBO H, O, the carbonate peroxyhydrates, e.g., 2Na CO 31b0,, and the phosphate peroxyhydrates preferably the sodium pyrophosphate peroxyhydrate Na,P O .2l-l,O,. The most suitable organic hydrogen peroxide addition compound is the urea peroxide CO(Nl-! .l-i O In a finished detergent composition of this invention there will often be added minor amounts of materials which make the product more attractive. The following are mentioned by way of example. Sodium carboxymethylcellulose can be added in minor amounts to inhibit soil redeposition. A tarnish inhibitor such as benzotriazole or ethylenethiourea can also be added in amounts up to about 2 percent. Fluorescers, perfumes and dyes, while not essential in the composition of the invention, can be added in small amounts. An alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjustors. There might also be mentioned as suitable additives: bacteriostats, sodium sulfate, sodium carbonate and bactericides. Corrosion inhibitors generally are also added. Soluble silicates are highly effective inhibitors and can be added to certain composition of this invention at levels of from about The following examples serve to illustrate, but not to limit the novel compositions of the present invention. All percentages in the examples are by weight. The enzymes mentioned, are commercial powdered enzyme products, containing 6-8 percent active material.

EXAMPLE I A stable, free flowing detergent composition, which can be stored under different climatological conditions for a long period of time, is preferred by slurrying in a crutcher the surface active agents, builders, electrolytes, carboxymethyl cellulose, toluene sulfonate, sodium sulfate, brightener and water; spray-drying the slurry; dry-mixing the perborate and copolymer with the spray dried granules; and atomizing the perfume onto the agglomerates. The end product consisting of:

9.30% linear alkylbenzene sulfonate sodium salt (average molecular weight of alkylbenzene 240-245) 26. 10% sodium tripolyphosphate,

3.40% fatty acid (derived from fish oil),

3.401% condensation product of tallow alcohol and l l rnols ethylene oxide per mol alcohol, 6.20% sodium silicate,

0.80% carboxymethylcellulose,

0.40% toluene sulfonate (sodium salt) 1.50% sodium salt of the maleic anhydride-vinyl methyl ether copolymer. (Specific viscosity of anhydride 0.4), qpp 13.20% sodium sulfate,

25.00% sodium perborate-tetrahydrate,

8.00% moisture,

2.10% brightener, perfume is then thoroughly mixed with an enzyme powder to obtain a finished product containing 0.60 parts by weight of AL- CALASE" (Novo lndustri A/S, Copenhagen, Denmark).

Stored under severe conditions 8 weeks at 37 C. and percent relative humidity, the pourability and color of the detergent composition does not change and no noticeable loss in enzyme activity occurs.

Other suitable compositions are:

EXAMPLE ll 25% sodium coconut alcohol sulfate,

65% sodium tripolyphosphate,

25% sodium tripolyphosphate,

1.00% enzyme product* 1 .00% carboxymethylcellulose,

3.60% sodium toluene sulfate,

2.00% sodium salt of maleic anhydride-vinyl methyl ether,

200% sodium slat of maleic anhydride-vinyl methyl ether,

27.00% sodium sulfate,

2.00% sodium chloride,

2.90% miscellaneous,

7.50% moisture.

'ALCALASE; when Monsanto DA- 10 (40 percent active protease) replaces the "ALCALASE" on an equal weight basis. similar results are obtained, except greater enzyme activity.

EXAMPLE 111 6.00% linear alkylbenzene sulfonate-sodium salt (average C-atoms) of alkyl radical 1 1.9),

3.00% tallow alcohol sulfate sodium salt,

2.60% tallow alcohol ethylene oxide (9-12) condensate,

3.50% hydrogenated fatty acids derived from fish oil (average mol. wt. 285),

32. 10% sodium tripolyphosphate,

7.00% sodium silicate,

28.30% sodium perborate tetrahydrate,

6.10% sodium sulfate,

2.00% sodium salt of maleic anhydride-vinyl methyl ether,

2.00% miscellaneous,

7.40% moisture.

The copolymer may be replaced by the sodium salt of maleic anhydride-ethylene, or by the ethanolamide derivative of the maleic anhydride-vinyl methyl ether copolymer.

EXAMPLE 1V 7.00% sodium-3-(N,N-dimeghyl-N-tetradecylammonio)-2- hydroxypropane-l-sulfonate,

40.00% sodium tripolyphosphate,

25.70% sodium perborate tetrahydrate,

9.50% sodium sulfate,

4.50% sodium salt of maleic anhydride vinyl methyl ether,

8.70% sodium silicate,

3.00% enzyme product (ALCALASE), balance moisture EXAMPLE V EXAMPLE -Vl 6.50% sodium alkylbenzene sulfonate (average C-atoms in alkyl radical: 12)

9.70% sodium soap of rape seed oil fatty acid (C 52%, C20 1 30.20% sodium tripolyphosphate,

8.60% sodium silicate (SiO Na,0 2.6),

7.30% sodium sulfate,

24.40% sodium perborate tetrahydrate,

7.50% moisture,

0.70% enzyme product (ALCALASE),

3.0% miscellaneous (dyes, perfumes...

2.10% butanol ester of maleic anhydridevinyl methyl ether copolymer (specific viscosity of copolymer in anhydride form: 0.467).

The foregoing description and examples describe and illustrate certain preferred embodiments of the present invention.

It is not intended that the invention should be so limited, since 55 variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

What is claimed is: l. A granular, free flowing detergent composition consisting essentially of, calculated on a finished product basis:

from 10% to about by weight of a water-soluble inorganic builder salt, a water-soluble organic builder salt, or mixtures thereof; from about 0.01% to about 5% by weight of an enzyme product; from about 0.1% to about 8% by weight of a water-soluble alkali-metal salt, ester, or C alkylor alkylolamide of a copolymer of maleic anhydride and a vinyl compound of the formula RCH HCR. wherein one R renresents a hydrogen atom while the other R represents a C alkyl ether radical, or a hydrogen atom. and wherein the ratio of the maleic anhydride and vinyl compound in the copolymer is from 2:1 to l :2 and wherein the specific viscosity of the anhydride form of the copolymer where R represents a C alkyl ether radical is between 0.1 and 60 and the viscosity of the anhydride form of the copolymer when R represents a hy rogen atom is between 1.2 centipoises and 10 centipoises; and

from 0% to about 50% by weight of an organic, water-soluble surface-active agent selected from the group consisting of anionic, nonionic, amphoteric, and zwitterionic detergents and mixtures thereof.

2. A composition of claim 1 which also contains from 5% to about 50% by weight of a hydrogen peroxide addition compound.

3. A granular free flowing detergent composition consisting essentially of:

from 5 to 25 percent by weight of a water-soluble anionic detergent;

from 10 to 50 percent by weight of water-soluble inorganic builder salt;

from 8 to 38 percent by weight of a water-soluble inorganic hydrogen peroxide addition compound;

from 0.1 to 3 percent by weight of an enzyme product; and

from 0.3 to 5 percent by weight of a water soluble alkalimetal salt of a maleic anhydride-vinyl methyl ether copolymer, wherein the ratio of the maleic anhydride and vinyl compound in the copolymer is from 2:1 to 1:2 and the anhydride form of the copolymer has a specific viscosity between 0.1 and 6.0.

4. A composition of claim 3 wherein the hydrogen peroxide addition compound is sodium perborate tetrahydrate.

5. A composition of claim 4 wherein the copolymer derivative is the sodium or potassium salt of the aleic anhydridevinyl methyl ether copolymer.

6. A composition of claim 4 wherein the copolymer derivative is a diethanolamide.

553 33 I UNITED STATES PATENT OFFICE 615 (Q 7 CERTIFICATE OF CORRECTION Patent No. 3,655,568 Dated April 11, 1572 Wahib Nassif Zaki; Jean Marie Louis Coulomb;

Inventor(s) Peter Lovo'ren It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Under "Abstract" line 5, "alkylolomide" should read alkylolamide-. Col. 1, line 60, "an should be a. C01. 2, line 30, delete last two words in the line "alkyl-or" Col. 3, line 8, "as" should be is--; line 15, first item under Component B reads "950%" it should be 9. 50%-; line 41, "X 32 sodium" should read -X sodium--;

line 45, "use" should be --used--. Col. 5, line 2, "frees flowing" should be --freeflowing--. Col. 7, line 9, "enzymes should be enzyme--;

Col. 10, line 27, 3.401%" should be 3.400%--; between lines- 28 & 29, add -6. 20% sodium silicate-; delete line 48 which reads "65% sodium tripolyphosphate" delete line 55 which reads "200% sodium salt of maleic anhydride vinyl methyl ether" 7 line 66, after "atoms" delete Claim line 2, "aleic" should be t-maleic'-.

Signed and sealed this 12th day of September 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents $225 UNITED STATES PA ENT OFFICE CERTIFICATE OF CORRECTE Patent No. 3, 655, 568 Dated I April 11, 1972 Wahib Nassif Zaki; Jean Marie Louis Coulomb; Inventor(s) Peter L-ovqren It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Under "Abstract" line 5, "alkylolomide" should read alkylol amide-- Col. 1, line 60, "an" should be a. C01. 2, line 30, delete last two words in the line "alkyl-or" Col. 3, line 8, "as" should be ---is-; line l5, first item under Component B reads "95O% it should be 9. 50%-,- line 41, "X 32 sodium" should read X sodiumline 45, "use" should be used--. Col. 5, line 2, frees flowing" should be --freeflowing--. Col. 7, line 9, "enzymes" should be enzyme;

Col. 10, line 27, "3.401%" should be 3 .40Os--: between lines 28 & 29, add 6.20% sodium silicate-; delete line 48 which reads 65% sodium tripolyphosphate" delete line 55 which reads "200% sodium salt of maleic anhydride vinyl methyl ether" 7 line 66, after "atoms" delete Claim line 2, "aleic" should be -,maleic'.

Signed and sealed this 12th day of September 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. A composition of claim 1 which also contains from 5% to about 50% by weight of a hydrogen peroxide addition compound.
 3. A granular free flowing detergent composition consisting essentially of: from 5 to 25 percent by weight of a water-soluble anionic detergent; from 10 to 50 percent by weight of water-soluble inorganic builder salt; from 8 to 38 percent by weight of a water-soluble inorganic hydrogen peroxide addition compound; from 0.1 to 3 percent by weight of an enzyme product; and from 0.3 to 5 percent by weight of a water-soluble alkali-metal salt of a maleic anhydride-vinyl methyl ether copolymer, wherein the ratio of the maleic anhydride and vinyl compound in the copolymer is from 2:1 to 1:2 and the anhydride form of the copolymer has a specific viscosity between 0.1 and 6.0.
 4. A composition of claim 3 wherein the hydrogen peroxide addition compound is sodium perborate tetrahydrate.
 5. A composition of claim 4 wherein the copolymer derivative is the sodium or potassium salt of the aleic anhydride-vinyl methyl ether copolymer.
 6. A composition of claim 4 wherein the copolymer derivative is a diethanolamide. 